Soap



llUUlll l; use: on A5673 x 2.162.255 F35 RGIGYEHQS II V V Patented June 13, 1939 2,162,255

SOAP

Robert F. Heald, Nutley, N. 'J., assig'nor to Colgate-Palmolive-Peet Company, Jersey City, N. 1., a corporation of Delaware No Drawing. Application April 27, 1938,

Serial No. 204,561 21 Claims. (01. 87-16) This invention relates to improved soaps, and than others, or are preferred because of their to methods of manufacturing improved soaps. It lower cost. relates more particularly to colored soaps, which The coloring materials which are stabilizedinthe owe their color either to the presence of natural presence of soap by tin compounds, such as those coloring material occurring in the fats or oils outlined above, include such naturally occurring from which the soap is made, such as the green coloring materials as chlorophyl, which occurs as coloring material of olive oil and the red coloring the primary coloring material in olive oiland is material of palm oil, or to which coloring maresponsible for the green color-of olive oil soaps, terial, such as synthetic dyestuffs, have been carotin and xanthrophyLwhich are the coloring added, th color of the improved colored soaps materials present in palm oil and are responsible of the present invention being stabilized by the for the red color of palm oil and soaps made from inclusion in the soap of a small amount of a tin unbleached palm oil, as well as the synthetic dyecompound, stuffs which are ordinarily used to color soaps, This application is in part a continuation of my including soaps made from bleached palm oil, prior application Serial No. 73,477, flled'Aprll 9, from cocoanut oil, from tallow, from other fatty g. materials, or from mixtures of such fatty ma- Colored soaps, as heretofore produced, have terials. The tin compound not nly, stabilize had a decided tendency to change color on storhe e olor ns materials in'their r n l c ndiage. For example, a toilet soap produced from tion when present in soap, but also have the bleached palm oil and olive oil, having a green p p y f s abili h color f pr d ts color due to the chlorophyl in the olive oil, tends which are obtained when such colorin materials to lose the bright green color it has when freshly as carotin and xanthrophyl are bleached. Thus made on storage because ofthe recurrence of the when bleached palm oil is used in soap, as in adr d colo originally res nt in the al oil, mixture with olive oil to make a soap containing 25 Other colored soaps, such as red soap chips propalm oil and olive oil constituents, and a small duced from unbleached palm oil, tend to lose their amount o 8 tin u d is nco p rated, the color on standing and to become whitish. In ch ri ic-re color f the p n ri i lly practically all colored soaps which depend f present in the palm oil does not recur. As a retheir color upon coloring matter naturally pressult, ps m y be a from bleached p i em; in the fatty materials from whi h th soaps and olive oil which have a green color due to the ar made or t whi h synthetic" dyestufis h natural coloring material of the olive oil, and been added, an objectionable change in color which, due to the presence of atin compound, do takes place on storage. not change color on standing because of a reap- In accordanoewith the present i v ti thi pearance of the red color characteristic of the change in color on storage of soaps of this charpalm oil or because of a change in color of the acter is prevented or inhihited by the addition of c lo ophyl of the olive oil. Similarly, Soaps made a small amount of a tin compound t t soap, from tallow and cocoanut oil, containing a syn- The invention includes both this new method of thetic dye Such as Rhodamine C010! stabilizing the color of such soap, and the colored dex' No. 749, CalcOC Yellow MXXX, C0101 Index 40 soaps containing a small amount or a tin com- No. 138, n phthol yellow, Color In ex No. pound and having a stabilized color. Caloozine d B Color nd 749,.Pontaeyl A mb of ti compounds h v be t t d, Fast Blue 13, naphthol green, Color Index No. 5, and found effective for the stabilization of color Du Pont Brilliant, Silk Blue, are Stabilized in of colored soaps, including stannic chloride, stanl r y th d t of a small t f a tin 4 nic sulfate, stannic myristate, stannic phosphate, comp stannic stearate, stannic oxide, starlrlic am- The chemical reactions which may occur when monium chloride, stannous chloride, stannous a tin compound,,such as tin chloride, tin sulfate, phosphate, stannous oxalate, and others. of or the like is added to soap are not clearly under-' these, stannic chloride, because it is the cheapest, stood. The compounds may react to form tin 0 is preferred, although its action is no better, and y es. or inSOlflblB tin soaps; but in any in some cases not quite-as good, as, for example, stannic sulfate, stannic myristate, stannous phosphate or stannous oxalate. There is some difference in behavior between the various tin compounds, and some are somewhat more effective case, the addition of a small amount of a tin compound effectively stabilizes the color of colored soaps. The action is apparently not that of an anti-oxidant, because the stannous compounds are reducing agents and the stannic compounds are oxidizing agents, while both are effective stabilizers. If the action were that of an anti-oxidant, itwould be expected that the stannous compounds would be far more effective than the stannic compounds; whereas in general, the

stannic compounds are more eifective than the stannous compounds.

The amount of tin compound used with the soap may vary over a relatively wide range, from as little as about 0.01% up to about 0.5%, calculated as percentage of tin based on the soap. In general, the larger amounts show a more marked improvement in the stability of the color of the soap than do the smaller amounts. The use of about 0.05% of a tin compound, calculated as tin,- produces a marked improvement in the soap, and while larger amounts may bring about a somewhat greater improvement, such improvement is not suifioient to warrant the additional cost of the extra tin compound.

The tin compound may be added to the soap in the crutcher, or subsequently in a soap mixer or amalgamator.

The invention will be further illustrated by the following examples which illustrate various colored soaps produced in accordance with the present invention, but it is not limited thereto.

Example 1.-0.2% of a 50% watersolution of stannic chiorideis added to dry soap chips containing from 8 to 12% water made from olive oil I and bleached palm oil in the proportions of 10 to 30 parts of olive oil to 70 to 90 parts of bleached palmoil. The solution is thoroughly admixed with the soap in the crutcher or in a soap mixer, oramalgamator, after which the usual perfume ingredients are added and the soap worked up in the usual way. The soap soproduced, when freshly made, cannot be distinguished from a soap similarly made, except without the addition of the tin chloride. After several weeks standing, the soap made with the tin chloride retains its fresh color, while a similar soap, made without the tin chloride, develops a brown or reddish color.

The tin chloride should be added to the soap before the perfume is added, and should not be admixed with the perfume, as it tends to interact with the perfume to destroy its odor and to produce a dark colored material.

The use of a tin chloride to stabilize the color of a colored soap is advantageous with various types of colored soaps, such as hard toilet soaps containing from 8 to 12% of water, as well as textile or shampoo soaps containing 30% or more of water, and soap chips or granulated soap containing 3 to 12% of water.

Example 2.-0.2% of a 50% water solution of stannic chloride is incorporated in dry soap chips containing 3 to 6% of water made from unbleached palm oil, and having a red color. The tin chloride is crutched into the liquid kettle soap, and the soap is processed in the usual manner to produce soap chips. The resulting red soap chips retain their color well on storage, whereas similar soap chips made without the tin chloride, bleach and turn white after three to six months storage.

Example 3.0.2% of a 50% water solution of stannic chloride is added to a green olive oil soap containing about 30% water, intended for use as a textile soap. The resulting green soap retains its color and fresh appearance on storage.

Example 4.0.2% of a 50% water solution of stannic chloride is added to a shampoo soap containing about 30% water and made from cocoanut oil and olive oil' in the proportions of 3 to 1. The resulting green shampoo soap retains its color well on storage.

Example 5.0 .2% of a 50% water solution of stannic chloride is added to dry soap chipscontaining 8 to 12% water made from bleached oils and containing a synthetic dyestuff, such as Rhodamine B or Du Pont Brilliant Silk Blue (Du Point ,Briliiant Silk Blue is the trade name of a synthetic dyestufi of the E. I. du Pont de Nemours Company) to color the soap. The solution is thoroughly admixed with the soap on a soap mixer or amalgamator, and the soap is worked up in the usual way to produce a milled toilet soap. The resulting colored soap retains its color well onstorage, without recurrence of the color of the bleached coloring matter.

Stannous chloride or other tin compound may be substituted for stannic chloride in any of the above examples to produce a soap of stable color. Although stannous chloride is not as effective as stannic chloride in stabilizing the color of soaps of the type with which this invention is concerned, it nevertheless produces a marked improvement in suchsoaps. It may be used in about the same amount as the stannic chloride, that is, amounts ranging from 0.025% or less up to 0.8% or more.

The following examples illustrate various colored soaps made from a white soap base pro- 'duced' from approximately three parts of tallow and one part of cocoanut oil, the soaps being colored with synthetic dyestuffs. The aging characteristics of each of the soaps is markedly improved by the inclusion of the stannic chloride solution.

Example 6.A yellow milled soap of the following composition is produced as in Example 5:

. Percent Settled white soap chips, 13.5% 1120.... 98. 890 Titanium dioxide 0. 112 50% stannic chloride solution 0.200

Calcocid Yellow MXXX, cone. 1% solution 0. 200

Naphthol Yellow, 2% solution 0.345 Lemon soap perfume 0.253

. Example 7.A pink soap is prepared as in Example 5 from the following constituents:

Example 8.A violet orchid soap is prepared from the following constituents, following the procedure of Example 5:

Percent Settled white soap chips, 13.5% H2O 98. 879 50% stannic chloride solution 0. 200 Calcozine Red BX, 0.5% solution 0. 381 Pontacyl Fast Blue 13, 2% solution 0. 190 Lavender soap perfume 0. 350

252; COMPOSiiiONS.

. i Percent Settled white soap chips, 13.5% H2O 98. 471 50% stannic chloride solution 0. 200

.Naphthol Green,-4% solution 0.259

Calcocid Yellow MXXX, cone. 1% solution 0. 063 Pine oil soap perfume l. 007

Example 9.-A pine green soap of the following composition isprepared by the procedure of Example 5:

The foregoing examples, that is. Examples 1 through 9, illustrate the use of tin chloride with various types of soap, and are intended to show by way of example the various types of colored soaps to which the present invention is applicable. It will be understood that in each of Examples 1 through 9 the stannic chloride may be replaced by stannous chloride, or by other tin compounds, such as stannic sulfate, stannic myristate, stannous tartrate, stannous oxalate, stannous oxide, stannic phosphate, stannic stearate, stannic oxide, stan'nic ammonium chloride, etc. In the following examples, the use of these various tin compounds with a particular soap is illustrated, it being understood that any of the tin compounds may be used with any of the soaps of the foregoing examples, with a marked improvement in aging characteristics of the colored soaps.

Example 10.-0.133% of stannic sulfate is added to. dry soap chips containing from 8 to 12% of water made from olive oil and bleached palm oil in the proportions of 10 to 30 parts of olive oil to '70 to parts of bleached palm oil. The solution is thoroughly admixed with the soap by crutching or in a soap mixer, or amalgamator, after which the usual perfume ingredients are added andthc soap is worked up in the usual way. The soap so produced, when freshly made, cannot be distinguished from a soap similarly made except without the addition of the stannic sulfate. After several weeks standing, the soap made with the stannic sulfate retains its fresh color, while a similar soap made without the stannic sulfate, develops a brown or -reddish color.

Example 11.--A soap is prepared as in Example 10, except that about 0.395% of stannic myristate is substituted for the stannic sulfate. The soap shows excellent aging characteristics.

Example 12.--A soap is produced as in Example 10, except that 0.074% of 'stannous tartrate is substituted for the stannic sulfate.

Example 13.-A soap is produced as in Example 10, except that 0.079% of stannous oxalate is substituted for the stannic sulfate.

Example 14.--A soap is produced as in Example 10, except that 0.052% of stannous oxide is substituted for the stannic sulfate.

Example 15.-A soap is produced as in Example 10, except that 0.120% of stannic phosphate is substituted for the stannic sulfate.

Example 16.-A soap is produced as in Example 10, except that 0.481% of stannic stearate is substituted for the stannic sulfate.

Example 17.-A soap is produced as in Example 10, except that 0.058% of stannic oxide is substituted for the stannic sulfate.

Example 18.-A soap is produced as in Example 10, except that 0.141% of stannic ammonium chloride is substituted for the stannic sulfate.

It will thus be seen that the present invention provides a process for the stabilization of the color of colored soaps containing natural coloring fimssiieierente oeuicu nuuu matter present in the fat or oil from which the I soap is made, or containing added synthetic dyestuffs, by the addition to the soap of a small amount of a tin compound; and also provides new and improved colored soaps, which include, in

addition to natural coloring matters or synthetic dyestuffs, a small amount of a tin compound to inhibit or prevent change in color of the coloring material, and improved colored soaps which not only contain such coloring materials but also ,contain residues resulting from the bleaching of natural coloring materials, the color of which is stabilized by the addition of a tin compound which not only stabilizes the coloring matter-present but also prevents a recurrence of the color of the bleached coloring matter.

I claim:

1. The method of tabilizing coloring materials when present in soap which comprises incorporating in the soap a small amount of a tin compound.

2. The method of stabilizing natural coloring material when present in soap which comprises incorporating in the soap a small amount of a tin compound.

3. The method .of stabilizing coloring material when present in soap which comprises incorporating in the soap a small amount of stannic chloride.

4. Colored soap in which a small amount of a tin compound has been incorporated to stabilize the color.

5. Soap, colored by a natural coloring material present in an oil or fat from which the soap, at least in part, is made, which coloring matter is stabilized by the addition of a small amount of a tin compound to the soap.

6. Colored soap in which a small amount of stannic chloride has been incorporated to stabilize the color.

'7. Colored soap in which a small amount of stannic sulfate has been incorporated to stabilize the color.

8. Colored soap in which a small amount of a tin soap has been incorporated to stabilize the color.

9. Green olive oil soap, stabilized in color by the addition of a small amount of a tin compound.

10. Red palm oil soap, stabilized in color by the addition of a small amount of a tin compound.

11. Green olive oil-palm oil soap, stabilized in color by the addition of a small amount of a tin compound.

12. The method of stabilizing the color of colored soaps, made, in part at least, from bleached oil ,or fat, to stabilize its color and to-prevent recurrence of the color ing material which comprises incorporating in the soap a small amount 'of a tin compound.

13. Colored soap, made from white stock, containing a synthetic dyestuff and stabilized in color by the addition of a small amount of a tin compound.

14. Colored soap containing a synthetic dyestuff and stabilized in color by the addition of a small amount of a tin compound.

15. Green olive oil soap, stabilized in color by the addition of a small amount of a tin chloride.

16. Green. olive oil-palm oil soap, stabilized in color by the addition of a small amount of a tin chloride.

17. Red palm oil soap, stabilized in color by the addition of a small amount of a tin chloride.

18. The method of stabilizing the color of green olive oil soap which comprises incorporating in the soap a small amount of a tin chloride 19. The method of stabilizing the color of red palm oil soap which comprises incorporating in the soap a small amount ofa tin chloride.

20. The method of stabilizing the color of green olive oil-palm oil soap and preventing the recurrence of the color of the palm oil, which comprises incorporating in the soap a small amount of a tin chloride.

21. Green soap, containing a substantial proportion of soap made from olive oil'and a substantial proportion of soap made from bleached palm oil, stabilized in color by the addition of a small amount of a tin chloride.

ROBERT F. HEALD.

CERTIFICATE OF' CORRECTION.

PatentNo. 2,162,255. June 13, 1939.

ROBERT F. HEALD.

It is hereby certified that error apbeare in the printed specificationof the above numbered-patent requiring correction as follows: Page}, sec- 0nd column, line 62, claim 15, before the word "stock" insert soap; and that the saidLetters Patent should beread with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this .L5th day of August, A. D. 1959.

Leslie Frazer (Seal) Acting Commissioner of Patents. 

